The {D,H}+complex in silicon, with D=P or As, is studied near theabinitioHartree–Fock level. The results show that the transitions between {D,H}0and {D,H}+involve a drastic change in the equilibrium geometry and electronic structure of the complex. The implications of these results on the observed dependence of the debonding rates on majority‐ and minority‐carrier concentrations for both As and P donors are discussed.